EP0161066B1 - Alliages à base de nickel/titane - Google Patents

Alliages à base de nickel/titane Download PDF

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Publication number
EP0161066B1
EP0161066B1 EP85302374A EP85302374A EP0161066B1 EP 0161066 B1 EP0161066 B1 EP 0161066B1 EP 85302374 A EP85302374 A EP 85302374A EP 85302374 A EP85302374 A EP 85302374A EP 0161066 B1 EP0161066 B1 EP 0161066B1
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EP
European Patent Office
Prior art keywords
alloy
warm
worked
titanium
annealed
Prior art date
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Expired
Application number
EP85302374A
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German (de)
English (en)
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EP0161066A1 (fr
Inventor
Tom Duerig
Keith Melton
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Raychem Corp
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Raychem Corp
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Publication date
Application filed by Raychem Corp filed Critical Raychem Corp
Priority to AT85302374T priority Critical patent/ATE47158T1/de
Publication of EP0161066A1 publication Critical patent/EP0161066A1/fr
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Publication of EP0161066B1 publication Critical patent/EP0161066B1/fr
Expired legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/006—Resulting in heat recoverable alloys with a memory effect

Definitions

  • This invention relates to the field of processing beta-phase nickel/titanium-base alloys and, more particularly, to the field of processing beta-phase nickel/titanium-base, shape-memory alloys.
  • the ability to possess shape memory is a result of the fact that the alloy undergoes a reversible transformation from an austenitic state to a martensitic state with a change of temperature. Also, the alloy is considerably stronger in its austenitic state than in its martensitic state. This transformation is sometimes referred to as a thermoelastic martensitic transformation.
  • An article made from such an alloy for example, a hollow sleeve, is easily deformed from its original configuration to a new configuration when cooled below the temperature at which the alloy is transformed from the austenitic state to the martensitic state.
  • the temperature at which this transformation begins is usually referred to as M s and the temperature at which it finishes M f .
  • GB-A-2117001 discloses a method of imparting a reversible shape memory effect to a nickel- titanium alloy, comprising cold-working the alloy into a predetermined size and shape, heat-treating the alloy at at least 600°C, and aging the alloy at a temperature below 600°C under mechanical constraint.
  • Shape-memory alloys have found use in recent years in, for example, pipe couplings (such as are described in U.S. Patent Nos. 4,035,007 and 4,198,081 to Harrison and Jervis), electrical connectors (such as are described in U.S. Patent No. 3,740,839 to Otte and Fischer), switches (such as are described in U.S. Patent No. 4,205,293), actuators, etc.
  • shape-memory alloys such as those illustrated in U.S. Patent No. 4,283,233 to Goldstein et al. may be readily cold worked followed by a warm anneal.
  • Other alloys such as those found in U.S. Patent No. 3,753,700 to Harrison et al., are subject to severe embrittlement when cold worked. These latter alloys are usually hot worked followed by a hot anneal.
  • An alternative treatment of these latter alloys would be working at liquid- nitrogen temperatures to take advantage of the increased ductility of the martensitic phase. Needless to say, such a treatment is impractical.
  • the deformed object is allowed to begin reversion to its original configuration without being restrained by a force of any great amount.
  • the coupling when heated is allowed to freely contract until constrained by the external dimensions of the pipe.
  • the present invention provides a method of processing a beta-phase nickel-titanium base alloy that is capable of undergoing a transition between austenitic and martensitic phases, comprising:
  • the invention increases the amount of work that can be obtained from a heat-recoverable, shape-memory alloy member when it it is subject to restraint by an applied force; the invention increases the amount of force that can be obtained from a rigidly restrained, heat-recoverable member by a method that is practically feasible; and the invention processes an alloy having limited cold ductility by a method that is practically feasible.
  • the annealing temperature is preferably in the same range as the working temperature.
  • the working and annealing temperatures are preferably in the range of about 350 to 600°C.
  • the prior art problem of limited cold ductility is overcome by controlling the working temperature so that it is sufficiently above room temperature that the alloy has improved workability (i.e., sufficient ductility) and that random disclocations in the microsructure of the alloy begin to rearrange into an ordered network of dislocations comprising essentially dislocation-free cells surrounded by walls of higher dislocation density. This prevents excessive work hardening on successive passes.
  • the working temperature should not be so high that the dislocations generated by the working are anihilated by a thermally activated climb/ glide process; thus the working temperature should be below that at which full recrystallization occurs.
  • a cell structure is produced in which the cell walls are very sharp and well defined.
  • the fine subgrains thus produced provide material with substantially higher austenitic yield strengths than conventionally hot-worked material, i.e., material where the working and annealing temperatures are above those at which recrystallization occurs.
  • the warm-worked material is preferably annealed at a temperature similar to the working temperature.
  • the material may be annealed at the same time due to the warm working so that a separate annealing step is not necessary and, in fact, is optional.
  • the preferred working and annealing temperatures of the alloy are in the range of about 350 to 600°C, it is most preferred that the working and annealing temperatures be about 500°C. It is also preferable that the alloy be annealed for about one hour.
  • the method of the invention may also include air-cooling the alloy to room temperature after the warm-working step. This may be necessary when the alloy is transferred from the place of warm working to the annealing oven.
  • the method of the invention further comprise a step of air-cooling to room temperature.
  • warm working of the alloy there are many forms of warm working of the alloy which will produce the desired objects of the invention. Preferred forms of warm working are drawing, swaging, or warm rolling. However, other similar types of warm working are also contemplated within the scope of the invention.
  • the method according to the invention while applicable to many different types of beta-phase nickel/titanium-base alloys and shape-memory alloys, has particular application to shape-memory alloys and most particular application to those types of shape-memory alloys which have limited cold ductility.
  • One alloy system having such limited cold ductility is the ternary shape-memory alloy comprised of nickel, titanium, and iron, as described in the above mentioned U.S. Patent No. 3,753,700 to Harrison et al.
  • the warm working and annealing of the alloy occur below the recrystallization temperature of the Harrison et al, alloy, which is about 550 to 600°C.
  • Two sets of articles were prepared from a ternary alloy of nickel, titanium, and iron.
  • the alloy had a nominal composition of Ti50Ni47Fe3 in atomic percent.
  • One set of articles was hot worked and annealed at 850°C.
  • Another set of articles was warm worked and annealed at 500°C.
  • Each set of specimens was strained at -196°C to total strains between 7 and 10%. The loading rate was 50 Newtons per second. After reaching the desired loads, the loads were ramped back to zero and the permanent strains were recorded. The specimens were then loaded to various loads and heated so as to effect recovery. During heating, the recovery was recorded.
  • Curve A represents those samples which were prepared according to the prior art. Those samples were the ones that were hot worked and hot annealed at 850°C.
  • Curve B represents articles prepared according to the method of this invention. These articles were warm worked and warm annealed at 500°C.
  • the difference between the two sets of articles is surprising and totally unexpected. It is evident that for any amount of load applied to the articles, the articles which were warm worked and warm annealed had a greater amount of recovery than those that were hot worked and hot annealed. Thus, the amount of work obtainable with the present invention is significantly greater than that available in the prior art. It is also evident that the amount of motion, or the amount of work that can be obtained decreases less fast with increasing load with the articles prepared according to the method of this invention than with the articles prepared according to the prior art method.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Thermal Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Heat Treatment Of Steel (AREA)
  • Catalysts (AREA)
  • Chemically Coating (AREA)
  • Forging (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Cell Electrode Carriers And Collectors (AREA)
  • Inert Electrodes (AREA)
  • Materials For Medical Uses (AREA)

Claims (8)

1. Procédé de traitement d'un alliage à base de nickel-titane en phase bêta qui est capable de subir une transition entre les phases austénitique et martensitique, comprenant les opérations qui consistent à:
(a) soumettre l'alliage à un travail à température modérée; et
(b) soumettre l'alliage à un recuit à température modérée; dans lequel les températures auxquelles l'alliage est soumis à un travail et à un recuit sont respectivement supérieures à environ 350°C et inférieures à la température à laquelle l'alliage est pratiquement totalement recristallisé.
2. Procédé suivant la revendication 1, dans lequel les températures sont comprises dans la plage d'environ 350° à environ 600°C.
3. Procédé suivant la revendication 2, dans lequel l'une des, ou les deux, températures sont égales à environ 500°C.
4. Procédé suivant l'une quelconque des revendications 1 à 3, qui comprend l'étape consistant à refroidir à l'air l'alliage, à température ambiante, après recuit.
5. Procédé suivant l'une quelconque des revendications 1 à 3, qui comprend l'étape consistant à refroidir à l'air l'alliage, à température ambiante, après l'avoir soumis à un travail mais avant de l'avoir soumis à un recuit.
6. Procédé suivant l'une quelconque des revendications 1 à 5, dans lequel l'alliage est travaillé par étirage, estampage ou laminage.
7. Procédé suivant l'une quelconque des revendications 1 à 6, dans lequel l'alliage est soumis à un recuit pendant environ une heure.
8. Procédé suivant l'une quelconque des revendications 1 à 7, dans lequel l'alliage est un alliage ternaire à mémoire de forme consitué de nickel, de titane et de fer.
EP85302374A 1984-04-04 1985-04-03 Alliages à base de nickel/titane Expired EP0161066B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT85302374T ATE47158T1 (de) 1984-04-04 1985-04-03 Legierungen auf nickel-titanbasis.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US06/596,771 US4502896A (en) 1984-04-04 1984-04-04 Method of processing beta-phase nickel/titanium-base alloys and articles produced therefrom
US596771 1984-04-04

Publications (2)

Publication Number Publication Date
EP0161066A1 EP0161066A1 (fr) 1985-11-13
EP0161066B1 true EP0161066B1 (fr) 1989-10-11

Family

ID=24388629

Family Applications (1)

Application Number Title Priority Date Filing Date
EP85302374A Expired EP0161066B1 (fr) 1984-04-04 1985-04-03 Alliages à base de nickel/titane

Country Status (6)

Country Link
US (1) US4502896A (fr)
EP (1) EP0161066B1 (fr)
JP (1) JPS60230967A (fr)
AT (1) ATE47158T1 (fr)
CA (1) CA1246970A (fr)
DE (1) DE3573618D1 (fr)

Families Citing this family (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4793382A (en) * 1984-04-04 1988-12-27 Raychem Corporation Assembly for repairing a damaged pipe
US4740253A (en) * 1985-10-07 1988-04-26 Raychem Corporation Method for preassembling a composite coupling
US4713870A (en) * 1985-03-26 1987-12-22 Raychem Corporation Pipe repair sleeve apparatus and method of repairing a damaged pipe
JPH02277752A (ja) * 1986-09-26 1990-11-14 Furukawa Electric Co Ltd:The 形状記憶・超弾性材料の熱処理方法
CH671583A5 (fr) * 1986-12-19 1989-09-15 Bbc Brown Boveri & Cie
USRE36628E (en) * 1987-01-07 2000-03-28 Terumo Kabushiki Kaisha Method of manufacturing a differentially heat treated catheter guide wire
FR2617187B1 (fr) * 1987-06-24 1989-10-20 Cezus Co Europ Zirconium Procede d'amelioration de la ductilite d'un produit en alliage a transformation martensitique et son utilisation
US5001446A (en) * 1988-08-01 1991-03-19 Matsushita Electric Works, Ltd. Shape memory alloy and electric path protective device utilizing the alloy
JPH07103457B2 (ja) * 1989-02-10 1995-11-08 トミー株式会社 形状記憶合金製矯正ワイヤーの形態付与方法
US6077368A (en) * 1993-09-17 2000-06-20 Furukawa Electric Co., Ltd. Eyeglass frame and fabrication method
US5540718A (en) 1993-09-20 1996-07-30 Bartlett; Edwin C. Apparatus and method for anchoring sutures
EP0753080A1 (fr) 1994-03-31 1997-01-15 Petrus Antonius Besselink Procede de traitement d'alliage nickel-titane-niobium et articles fabriques dans cet alliage
US6425829B1 (en) * 1994-12-06 2002-07-30 Nitinol Technologies, Inc. Threaded load transferring attachment
US5961538A (en) 1996-04-10 1999-10-05 Mitek Surgical Products, Inc. Wedge shaped suture anchor and method of implantation
US5843244A (en) * 1996-06-13 1998-12-01 Nitinol Devices And Components Shape memory alloy treatment
FR2758266B1 (fr) * 1997-01-16 1999-04-09 Memometal Ind Agrafe de contention ou d'osteosynthese et procede de fabrication d'une telle agrafe
FR2758338B1 (fr) * 1997-01-16 1999-04-09 Memometal Ind Procede de fabrication d'une piece superelastique en alliage de nickel et de titane
US6149742A (en) * 1998-05-26 2000-11-21 Lockheed Martin Corporation Process for conditioning shape memory alloys
US8562664B2 (en) * 2001-10-25 2013-10-22 Advanced Cardiovascular Systems, Inc. Manufacture of fine-grained material for use in medical devices
CN113025932B (zh) * 2021-03-02 2021-12-10 台州学院 一种细晶和均匀析出相gh4169镍基高温合金的制备方法

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3753700A (en) * 1970-07-02 1973-08-21 Raychem Corp Heat recoverable alloy
US4001928A (en) * 1973-01-04 1977-01-11 Raychem Corporation Method for plugging an aperture with a heat recoverable plug
US3953253A (en) * 1973-12-21 1976-04-27 Texas Instruments Incorporated Annealing of NiTi martensitic memory alloys and product produced thereby
US3948688A (en) * 1975-02-28 1976-04-06 Texas Instruments Incorporated Martensitic alloy conditioning
US4283233A (en) * 1980-03-07 1981-08-11 The United States Of America As Represented By The Secretary Of The Navy Method of modifying the transition temperature range of TiNi base shape memory alloys
JPS58151445A (ja) * 1982-02-27 1983-09-08 Tohoku Metal Ind Ltd 可逆形状記憶効果を有するチタンニツケル合金およびその製造方法

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
A.C. Guy, Metallkunde f. Ingenieure, Akad. Verlagsges. 1970, p. 366-373 *
ASM Metals Reference Book, 2. ed., Metals Park, Ohio, p. 58 *
G.E. Dieter, Mechanical Mewtallurgy 2. ed. (1976) McGraw, p. 239, 240 *

Also Published As

Publication number Publication date
JPS60230967A (ja) 1985-11-16
CA1246970A (fr) 1988-12-20
ATE47158T1 (de) 1989-10-15
US4502896A (en) 1985-03-05
DE3573618D1 (en) 1989-11-16
EP0161066A1 (fr) 1985-11-13

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